Color photographic materials



1968 MAKOTO YOSHIDA ETAL 3,409,439

COLOR PHOTOGR APHIC MATERIALS Filed Jan. 22, 1965 2 heets-Sheet l OPTICAL DENSITY '01 50o WAVE LENGTH (m 1.)

OPTICAL [JENSITY "o1 WAVE LENGTH (m u) INVENTORS' MAKOTO YOS HIDA BY MOMOTOSHI T5 (10A Nov. 5, 1968 MAKOTO YOSHIDA ETAL 3,409,439

COLOR PHOTOGRAP HIC MATERIALS 2 Sheets-Sheet 2 Filed Jan. 22, 1965 500 WAVE LENGTH (-m u.

' 500 WAVELENGTH (m u.

m up. 0 A Wm TRD NWO EH5 VST R mm m a 3 Z w Mm M MM wfi United States Patent 3,409,439 COLOR PHOTOGRAPHIC MATERIALS Makoto Yoshida and Momotoshi Tsuda, Odawara-shi, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa-ken, Japan, a corporation of Japan Filed Jan. 22, 1965, Ser. No. 427,417 Claims priority, application Japan, Feb. 1, 1964, 39/4 920 Claims. (61. 96-100) ABSTRACT OF THE DISCLOSURE A yellow-forming color coupler for use in photographic silver halide emulsion layers, having the general formula:

COOR

wherein R is a member selected from the class consisting of an alkyl group having at least 8 carbon atoms and an aliphatic residual group having at least 8 carbon atoms and having at least one ether bond; X is a member selected from the class consisting of a hydrogen atom and a halogen atom; and Y is a member selected from the class consisting of a hydrogen atom, a loweralkoxy group and a halogen atom.

porating in three or more photographic emulsions having different spectroscopic sensitivities, there are provided a process wherein a water-solubilizable group or 'an alkalisolubilizable group is introduced in the coupler molecule and the coupler is incorporated in the photographic emulsion as a solution in water or an alkaline solution, a proce ss wherein the coupler having oil-solubilizable group in its molecule so as to be dissolved in a Water-immiscible organic solvent is used and the coupler is incorporated in the photographic emulsion asa solution in a high-boiling point organic solvent, a process wherein the coupler having oil-solubilizable group in its molecule is incorporated in the emulsion as a low-boiling point organic solvent, a process wherein the couplers having oil-solubilizable group are incorporated in the emulsions by using high boiling point-and low boiling point organic solvents together, and a process wherein the coupler having oilsolubilizable group is incorporated in the emulsion without the use of any solvents.

It has been well known that in order to improve the stability of a colored image formed by the color development of couplers incorporated in emulsions to light, heat, and moisture in these color photographic materials, the use of the coupler having oil-solubilizable group whereby the coupler can be dispersed in the emulsion as a solution of a water-insoluble or slightly soluble organic solvent (hereafter, it is called a coupler solvent), that is, the use of a so-ca-lled protective coupler is desirable.

The protective coupler, in order to be used in the color photographic material, must fully suffice the photographic properties, such as, coupling efficiency of coupler, coupling rate, fogging, color tone of formed colored image, and the like as well as must have a sufiicient solubility in 3,409,439 Patented Nov. 5, 1968 a coupler solvent and a good dispersibi-lity in the emulsion. As such protective couplers, various compounds have been synthesized and patented, but they have no sufiicient solubility in coupler solvents or insufficient dispersibility in emulsions, or they are very expensive from a view point of synthesis and raw materials.

For example, the compounds having dialkylphenoxy group (e.g., United States Patent 2,875,057) or dialkylcyclohexyloxy group (e.g., United States Patent 2,920,- 961) have been provided, but the cost of the raw materials for the compounds is high.

Therefore, an object of this invention is to provide a color photographic material containing a novel yellow coupler which can be easily synthesized at an extremely low cost.

A further object of this invention is to provide a color photographic material containing a novel yellow coupler having improved photographic properties.

Other objects and advantages will become clear from the following descriptions.

The inventors have found improved yellow couplers that will be shown below, said couplers being produced by a simple synthetic process using easily available inexpensive raw materials. The yellow couplers in this invention are, as will be explained later in detail, novel compounds of an extremely low cost from the view point of raw materials and synthesis as well as having a sufficient solubility in coupler solvents and a good dispersibility in the emulsions. The couplers in this invention have excellent photographic properties, such as, coupling etficiency of coupler, coupling rate, fogging, color tone of obtained colored image and the like, and also the stability to light, heat and moisture of the formed colored image by using such a coupler is excellent.

That is, the invention relates to a color photographic material containing the yellow coupler having the following general formula:

COOR

wherein R is a member selected from the class consisting of an alkyl group (including the alkyl group having at least a side chain) having above 8 carbon atoms and an aliphatic residual group having above 8 carbon atoms and having one or more ether bonds, X is a member selected from the class consisting of a hydrogen atom and a halogen atom, and Y is a member selected from the class consisting of a hydrogen atom, a lower alkoxy group and a halogen atom.

As shown in the above general formula, the coupler of this invention has been substituted with carboxyl acid ester group having an alkyl group or more than 8 carbon atoms at the meta-position of the anilide nucleus. Therefore, the coupler can be prevented from being come out of the added emulsion layer by diffusion as well as the solubility of the coupler in coupler solvents and the dispersibility in the emulsion are excellent. That is, the coupler of this invention is provided with sufiicient conditions necessary for a color photographic coupler even though it is substituted with such a simple substituent.

Further, the coupler of this invention has a lower alkoxy group or a halogen atom at the ortho-position of the anilide nucleus, and this gives remarkable effects for improving the photographic properties, such as, coupling efliciency of coupler, coupling rate, color tone of the formed colored image, etc., and show extremely desirable yellow.

Moreover, the raw materials, necessary for the syntheisis of the couplers, such as, benzoyl acetate, 3-amin o- 4-methoxy benzoic acid, 3-amino-4-chlorobenzoic acid, the esters thereof, and lauryl alcohol are generally manufactured in a large scale as the raw materials for general organic compounds and hence easily available at a low cost. Also, it is easily understood that the cost of couplers TABLE 1 C 0 OR 6-0 0 CHQCONH Solubility, g./l00 g. solvent 0:) Structural Y R formula weight Dibutyl Tributyl Ethyl phthalate phosphate acetate C3H17 425 88 28. 2 -CIOH21 453 15 4O 26. 8 -C12H:5 481 21 61 22. 4 C14H2o 509 23 53 29. 4 -C1eHsa 537 24 56 20. 8 -C8Hl7 429. 5 7 25 15. 11 1oH21 457. 5 2 8 10. 5 -C12H35 485. 5 1. 5 1. 0 5. 2 CH2QH(C2H (CH2) 0H; 420. 5 41 110 23. 8 -(CH2)1CH(CH:)2 57. 5 80 163 47. 6

of this invention are very cheap, as will be shown later in the examples for synthesis thereof, from the fact that the couplers of this invention can be produced in two or three steps by using such extremely inexpensive raw materials.

It is clear that when a same weight of a coupler is added in the case of dispersing a coupler in an emulsion, the use of a coupler having a smaller molecular weight improves, in general, the coupling efficiency since the mole ratio of coupler to the addition amount increases as the molecular weight of the coupler to be added decreases. The molecular weight of the coupler in this invention is, if, in the above-mentioned general formula, X is a hydrogen atom, R is a dodecyl group showing surficient diffusion resistance, and Y is a methoxy group (Structural Formula V) or a chlorine atom (Structural Formula XIII), 481 or 485.5 respectively, and is about 13% lower than that of a yellow coupler having dialkylphenoxy group, e.g., the coupler shown by the following structural formula:

OCH:

s u(t) having a molecular weight of 558. From the above fact, it will be clear that the coupler of this invention is very desirable for use and gives a good coupling efficiency and a yellow image having a high density.

Further, the inventors have found, as the results of investigations for reducing the molecular weight of the couplers of this invention and increasing the coupling efiiciency, that when an octyl group having 8 carbon atoms used as R, the coupler shows a suflicient diffusion resistance and can be used practically without being accompanied with any troubles as well as the coupler has also an excellent solubility in coupler solvents and dispersibility in the emulsions.

Then, if X is a hydrogen atom, R is an octyl group, and Y is a methoxy group (Structural Formula III) or a chlorine atom (Structural Formula XI) in the compound Further, it is also clear that, in the case of dispersing a coupler in an emulsion, a larger amount of the coupler can be dispersed in the emulsion as the solubility of the coupler in a coupler solvent is better and hence the use of such a coupler increases generally the coupling efl'iciency and gives a colored image having a high density. Since the couplers of this invention show excellent solubilities, as shown in the above table, in coupler solvents, in particular, in esteric organic solvents, such as phthalic acid esters, phosphoric acid esters, and acetic acid esters, and then the deposition of the coupler crystals when the solution of the coupler is in a super cooled state, is extremely small or slow, the use of such couplers is very profitable. However, in the case where X is a hydrogen atom and Y is a chlorine atom (Structural Formulas XI, XII and XIII) in the above-mentioned general formula, the melting point of the coupler is increased 22-36 C. higher than that of the coupler wherein Y is a methoxy group even though R is the same in both cases, and the solubility of the coupler in a coupler solvent is reduced less than /3 of that of the coupler having the methoxy group as R.

The inventors have found also, as the results of the investigations about the improvement of the solubility in coupler solvents of the coupler in which Y is a chlorine atom, that by using an alkyl group having side chains as R instead of using a straight-chain alkyl group, the melting point of such a coupler can be reduced and the solubility in coupler solvents can be remarkably improved. That is, by using an aliphatic alcohol having side chains, such as, commercially available 2-ethylhexanol, isodecyl alcohol or triisodecyl alcohol instead of using a straight chain aliphatic alcohol, the coupler suitable for the purposes can be easily synthesized and the solubility of the coupler in coupler solvents can be extremely increased as shown in Table 1.

Thus, if a coupler having an extremely better solubility in coupler solvents is used, the density of a colored image, color tone, transparency, and the stability to light, heat and moisture of the color photographic material are clearly improved remarkably.

In addition, the carbon number of R in the abovementioned general formula may be an odd number but on considering the availability, purity, and cost of them, it is naturally more profitable that the carbon number of R be an even number.

(wherein each of m, n and p is an integer larger than 1 and m+mg7) such as diethyleneglycol monobutyl ether and the like. In general, it will be easily understood that higher alcohols having more than 8 carbon atoms can be successfully used as the raw materials for introducing R.

As will be shown in Synthesis 3 later, the coupler of this invention has the feature that one active methylene hydrogen atom in the molecule can be easily replaced with a halogen atom. Since the halogen atom-substituted coupler of this invention forms a dye by 2 equivalents of silver ions at coupling, the coupler has an advantage that the dye can be formed with a half of silver ions as compared with the coupler. wherein the active methylene hydrogen atom is not replaced with a halogen atom.

The numerical values for the solubility shown in Table 1 are ones obtained at room temperature, but the solubility increases rapidly as the temperature increases and a large amount of the coupler can be dissolved in a small proportion of the coupler solvent at a raised temperature. The fact that the solubility of a coupler in a coupler solvent is high is an important property for a processwherein the coupler is dissolved in the coupler solvent, the solution is then dispersed in gelatin, and the dispersion is added in a photographic emulsion. Such addition processes for couplers will be explained later, in particular, a process for using only a high boiling point solvent in Examples 3, 5, and 9; a process for using a low boiling point solvent in Examples 7 and 8; and a process for using both solvents in Examples 1 and 2.

The above-mentioned addition process is the case where the coupler of this invention is dissolved in a coupler solvent, the solution is dispersed in gelatin and the dispersion is added in a photographic emulsion, but the addition of the coupler of this invention is not limited to the above case but the coupler may be added to other process. For example, the coupler having a low melting point may be fused into a liquid by heating and then dispersed in gelatin. The present addition process will be explained practically in Example 6. As other adding process, the coupler may be added in a photographic emulsion as an alkaline aqueous solution of it. This process will be explained practically in Example 4.

The couplers of this invention incorporated in silver halide photographic emulsions by the various processes as described above show very excellent coupling by a color developer mainly consisting of N,N-disubstituted paraphenylenediaminic developer and provide color photographic materials having excellent photographic properties.

The yellow image formed by the couplerof this invention has a good transparency and color reproducing property, and shows a strong absorption spectrum to a blue light of 400-480 millimicronsbut shows no harmful absorption spectrum to a green light of 500-600 millimicrons which is a cause for giving reddish tonein the yellow tone of the image, these properties of which are extremely preferable light absorption characteristics for color photography. The light absorption curve will be shown in Examples 1, 2, 3 and 5.

Yellow colored images obtained from yellow couplers that have been usually used in conventional color photography are easily influenced and faded by the external conditions such as light, heat and moisture, and colorphotographs obtained by using such a conventional coupler are frequently discolored during storage. On the other hand, the yellow colored image obtained by using the yellow coupler of this invention is extremely fast and stable and scarcely faded and discolored by the influences of light, heat, moisture, and chemicals. In particular, among the couplers of the above general formula, a coupler having a chlorine atom at the ortho-position of the anilide nucleus isparticularly fast and stable to light.

The couplers of this invention are not limited to the use for color photography but can be used for obtaining 2-col0r images or mono-color images as well as for print- L As the yellow couplers of this invention, the following examples are illustrated.

COOCgHn C O CHzCONH C Ha I (III) C OOCroHzr C O CH2CONH- OCH;

COOCnHas C O CHrCONH- COCHgCONH C 00 C H (VII) 0 0 O C isHsr C O C HzCONH (VIII) COCHrCONH CzHs (IX) 0 OOCmHrs C OCHaCONH- C 00 C I-I17 CO OCmHgr o oomooNH 1 I (XII) -o OCHzCONHO cooomomomnon, zHs c ooniooNH- 1 (XIV) CH3 ooownmen H; -o OCHzCONH- Cl (XV) CHa eooorn: (01197011; CH: -o OCHzCONHQ l (XVI) (JOOCnHia I F (XVII) F (XVIII) CH3 (XIX) (300 012B 0- 0 5 Cl (5 CH1 (XX) C OOC 14H (XXI) (300 C ill-I15 0 CH3 (XXII) The examples for synthesizing the couplers of this invention are as follows.

Synthesis 1 (1a) Dodecyl-3-amino-4-rnethoxy benzoate:

A four-necked flask of 1 liter was equipped with an agitator, a thermometer, an inlet pipe for nitrogen gas, and a distilling pipe for distilling lay-produced methanol and in the flask was charged 181 g. (1 mole) of methyl- 3-amino-4-methoxy benzoate and 279 g. (1.5 moles) of n-dodecyl alcohol. The charged materials were fused by heating 80 C.'in the inside temperature, added with 2.5 ml. of titanium butoxide, and by-produced methanol was distilled off by introducing a nitrogen gas. The system was further heated to maintain the inside temperature at 170-180" C., whereby the ester exchange reaction proceeded slowly and methanol began to distill off, and after 4 hours about of the theoretical amount of methanol was distilled off. Then, the system was cooled slowly and when the inside temperature reached 4050 C., the product was withdrawn from the flask and added into '1 liter of methanol. By standing alone the solution for one night, brown crystals were deposited, which were filtered by suction, washed with 500 rnl. of methanol and dried to give dodecyl-3-amino-4-methoxy benzoate. The yield was 271 g. (81%) and melting point of the product was 47- 48 C.

(1b) Benzoylaceto-Z-methoxy-5-dodecyloxycarbonyl anilide (Structural Formula V):

A three-necked flask was equipped with an agitator, a thermometer, and a pipe for distilling by-produced ethanol, and in the flask was placed 192 g. (1 mole) of ethylbenzoyl acetate and 335 g. (1 mole) of dodecyl-3-amino- 4 methoxy benzoate obtained in Synthesis 1. When the system was maintained at -160 C. in the inside temperature with stirring by heating, methanol began to distill off and about 60% of the theoretical amount of ethanol was distilled oif over about 6 hours. Then the agitator was removed and ethanol was further distilled off for another 30 minutes under a reduced pressure. The system was then cooled slowly, product was withdrawn and added in 2 liters of petroleum ether. By standing it alone for one night, yellowish white crystals were deposited. The crystals were filtered by suction, washed with 1 liter of petroleum ether, and recrystallized by using 1.7 liter of ligroin to give benzoylaceto-Z-methoxy-S-dodecyloxy carbonyl anilide. The yield was 317 g. (66%) and the melting point was 75-76 C.

Synthesis 2 (2a) Dodecyl-3-amino-4-chlorobenzoate:

The synthesis (la) mentioned above was carried out by using methyl-3-amino-4-chlorobenzoate instead of methyl-3-amino-4-methoxybenzoate, and thus obtained crystals were subjected to a recrystallization with methanol to give dodecyl-S-amino-4-chlorobenzoate. The yield was 79% and the melting point of the product was 60-62 C.

(2b) Benzoylaceto-2-chloro-5-dodecyloxycarbonyl anilide (Structural Formula XIII):

In the aforementioned synthesis (1b), dodecyl-3- amino-4-chlorobenzoate was used instead of dodecyl-3- amino-4-methoxybenzoate. Thus obtained crystals were subjected to a recrystallization by using ligroin to give benzoylaceto-Z-chloro-S-dodecyloxycarbonyl anilide. The yield was 60% and the melting point of the product was 98-100 C.

Synthesis 3 Benzoylchloroaceto-2-methoxy-S-dodecyloxycarbonyl anilide (Structural Formula XX) In a 500 ml. three-necked flask equipped with an agitator and a thermometer, were placed 48.1 g. (0.1 mole) of benzoylaceto-Z-methoxy-S-dodecyloxycarbonyl anilide and 250 ml. of chloroform, and they were dissolved under agitation. While maintaining the inside temperature at 5-10 C., 14.8 g. (0.11 mole) of sulfuryl chloride was added into the system dropwise. After agitating for about 3 hours while keeping the inside temperature at 10 C., chloroform was distilled off under low temperature and low pressure. When 400 ml. of acetonitrile was added and the system was allowed to cool in a cold place, white crystals were deposited. The crystals were recovered by filtration and subjected to a recrystallization by using 300 ml. of petroleum ether to give benzoylchloroaceto-Z- methoxy-S-dodecyloxycarbonyl anilide. The yield was 37 g. (72%) and the melting point of the product was 74-75 C.

The following table shows the melting points and the results of nitrogen analysis of the typical examples of the yellow couplers of the present invention.

TABLE 2 Structural N-analysis formula X R Y M.P., C

Calcd. Found -CaH17 -0CH3 58-60 3. 30 3. 40 CmH21 --0CH 75-76 3. 09 3. 11 C12H25 0CH3 75- 76 2. 91 2. 86 -C14Hzp 'OCH3 71-72 2. 75 2. 78 -CuH ooH3 77-79 2. 61 2. so --C1sH37 -OCH3 S082 2. 48 2. 59. CgH -Cl 94-95 3. 26 3. 11 C1nHg1 ----CI 97-98 3. 06 2. 91 Cr2H2s -Cl 98l00 2. 89 2. 59 CH2CH(C2H5) (011930113 -01 71-73 3.26 3. 2e (CH2)1OH(CH;)2 Cl 60-62 V 3. 06 2. 93 CH2C (CH3)2(CH2)1CH3 -Cl 85-86 2. 89 3. 02 (CH2)20(CH2)20(CH2)3CH3 0CHa 73-75 3. 06 2. 93 H2 0CH 7445 2. 71 2. 73

The examples of this invention are as follows:

Example 1 Into a mixture of 1.2 ml. of dibutyl phthalate, 3.0 ml. of ethyl acetate, and 0.8 m1. of isopropanol were dissolved by heating 4.0 g. of the coupler shown by the above-mentioned structural Formula V and 0.8 g. of a copolymer of vinylpyrolidon and vinyl acetate (mole ratio 7:3), and the solution was added in ml. of a 10% gelatin aqueous solution containing 2.0 ml. of a 10% aqueous solution of sodium alkylbenzene sulfonate. The system was subjected to a high speed agitation of 3 minutes at 40-50 C. with an interval of one minute intermittence for 5 times by means of a homo-blender to give an emulsified dispersion of the coupler, the polymer, and the gelatin. (Cf. Japanese patent application No. 38/ 29,792, if necessary.)

The total amount of the emulsified dispersion was mixed with a gelatin silver halide emulsion containing 4.5 g. of silver bromide and 7.5 g. of gelatin, and the mixture was applied on a film base of cellulose acetate followed by drying to give a color photographic material. The color photographic material was exposed and subjected to a color development with a developer having the following composition:

G. 4-N,N-diethylaminoaniline 2.0 Sodium sulfite (anhydrous) 5.0 Sodium carbonate (monohydrate) 20.0 Potassium bromide 2.0

Water to make 1 liter.

Thus developed color photographic material was then treated with the following bleaching solution and fixing solution and then dried.

Bleaching solution: G. Potassium ferricyanide 100 Boric acid 7.5 Potassium alum Water to make 1 liter.

Thus obtained yellow-colored film had the absorption image was stable to heat and moisture and the obtained film was extremely transparent.

Example 2 In this example, the coupler shown by the above-mentioned Structural Formula XIII was used instead of the coupler shown by the Formula V in Example 1, and the color photographic material in this case was also treated as in Example 1.

Thus obtained yellow-colored film had the absorption spectrum as shown in FIG. 2, which showed a clear yellow color having a reduced absorption spectrum over igreen portions. Also, it was confirmed that thus obtained yellow image was stable to light, heat and moisture and could be preserved for a long time.

Example 3 Two grams of the coupler shown by the above-mentioned Structural Formula V was added with 4 g. of dibutyl phthalate and the mixture was heated. v

- The above-mentioned coupler solution was added into 30 ml. of a 7% gelatin solution containing 0.1 g. of sodium dodecylbenzene sulfonate and the mixture was emulsified by agitating for 10 minutes with a high speed at 60 C. in a homo-blender.

The whole of the above-mentioned emulsion was added into '100 g. of a photographic emulsion containing 5 g. of silver bromide and 6 g. of gelatin and the mixture was applied on a film base followed by drying to (give a color photographic material. After exposure, the material was subjectedto a color development with a developer having the following composition:

G. Z-methyl-4-N,N-diethylaminoaniline 2.0 Sodium sulfite (anhydrous) 5.0 Sodium carbonate (mono-hydrate) 20.0 Potassium bromide 2.0

Water to make 1 liter.

Thus developed photographic material was thentreated with the bleaching solution and the fixing solution as in Example 1, and dried.

Thus obtained yellow-colored. film had the adsorption spectrum as shown in FIG. 3, that is, showed a visually desirable clear yellow having little reddish tone. Thus obtained yellow colored image was stable to heat and moisture.

The results of a fading test by heat and moisture of thus obtained colored image are shown in the following table comparing with the results of a yellow-colored Yellow Density Fading Yellow Coupler initial after percentoptieal days age density Coupler of Formula V 1. 1. 15 4 3, S-dicarboxy((4-stearoylmonoamide)- benzoybacetoanilide 1. 0.

Example 4 A mixture of 2 g. of the coupler shown by the abovementioned Stnuctural Formula V, 6 ml. of l N. sodium hydroxide aqueous solution, and 16 ml. of methanol was heated to form a solution and the solution was added with water to make 40 ml. of the whole solution, a 5% coupler solution. The whole of the above-mentioned coupler solution was added into 100 g. of a photographic emulsion containing 5 g. of silver bromide and 6 g. of gelatin and then the solution was neutralized with the addition of 1 ml. of a 2% citric acid. Thus prepared emulsion was applied on a film base, dried and treated as in Example 3.

Thus, a clear yellow image having the maximum absorption spectrum at 448 m. microns was obtained.

Example 5 Instead of the coupler having the Structural Formula V used in Example 3, a coupler having the Structural Fonmula XIII was used. Two grams of the coupler was dissolved into 6 g. of dibutyl phthalate by heating and then by emulsifying and coating as in Example 3, a color photographic material was obtained. The photographic material was exposed, and developed as in Example 3.

Thus obtained yellow-colored film had the absorption spectnum as shown in FIG. 4, that is, showed a visually desirable clear yellow tone having little reddish tone. Thus obtained yellow-colored image was stable to light, heat and moisture and could be preserved for a long time.

The results of a fading test by light, heat and moisture of the yellow image are shown in the following table comparing with a yellow-colored image obtained by using 3,5 dicarboxy-((4-stearoylmonoamide)benzoyl) acetoanilide.

FADING TEST BY LIGHT [5 hours irradiation by 1.5 kw. xenon lamp (6,500 K.)]

Yellow Density Fading Yellow Coupler initial after 5 percentoptical hours ago density Coupler having Formula XIII 1. 10 1. 01 8 3, S-dicarboxy- (4-stearoylmonoamide) I behzoyDacetoanilide 1. 05 0. 68 35 FADING TEST BY HEAT AND MOISTURE Example 6 Two grams of the coupler (M.P. 71-73 C.) having the above-mentioned Structural Formula XIV Was melted by heating, added in 30 ml. of a 10% gelatin solution containing 0.2 g. of sodium dodecylbenzene sulfonate, and

the mixture was subjected to a high-speed agitation at C. for 10 minutes in a homo-blender to form an emulsified dispersion.

The whole of the above emulsion was added into g. of a photographic emulsion containing 5 g. of silver bromide and 6 g. of gelatin, and the mixture was applied on a film base to give a color photographic material, which was exposed and developed as in Example 3.

Thus, a clear yellow colored image having the maximum absorption spectrum at 445 m. microns was obtained.

Example 7 Two grams of the coupler having the above-mentioned Structural Formula XIV was dissolved into 4 ml. of ethyl acetate by heating, the solution wasadded in 30 ml. of a 7% gelatin solution containing 0.1 g. of sodium dodecylbenzene sulfonate, and the mixture was agitated with a high speed at 50 C. for 10 minutes to give an emulsified dispersion. From thus prepared emulsion, a color photographic material was obtained as in Example 6. The photographic material was exposed and developed as in Example 3.

Thus, a clear yellow-colored image having the maximum absorption spectrum at 445 m. microns was obtained.

Example 8 Instead of the coupler having the Structural Formula XIV used in Example 7, a coupler having the Structural Formula XX was used. By emulsifying and coating the coupler as in Example 7, a color photographic material was obtained, which was exposed and developed as in Example 3.

Thus, a clear yellow colored image having the maximum absorption spectrum at 443 111. microns was obtained.

Example 9 Instead of the coupler having the Structural Formula V used in Example 3, a coupler having the Structural Formula XX was used. Two grams of the coupler was dissolved in 6 g. of dibutyl phthalate by heating and the solution was emulsified and coated on a film base as in Example 3 to give a color photographic material.

Thus, a clear yellow colored image having the maximum absorption spectrum at 448 m. microns was obtained.

What is claimed is:

1. A color photographic material comprising a support and at least one silver halide photographic emulsion layer containing a coupler having the following general formula COOR Q- w -Q wherein R is a member selected from the class consisting of an alkyl group having at least 8 carbon atoms and an aliphatic residual group having at least 8 carbon atoms and having at least one ether bond; X is a member selected from the class consisting of a hydrogen atom and a halogen atom; and Y is a member selected from the class consisting of a hydrogen atom, a lower alkoxy group and a halogen atom.

2. The color photographic material as claimed in claim 1 wherein said coupler is benzoylaceto-2-methoxy-5- dodecyloxycarbonyl anilide.

3. The color photographic material as claimed in claim 1 wherein said coupler is benzoylaceto-Z-methoxy-S-tetradecyloxycarbonyl anilide.

4. The color photographic material as claimed in claim 1 wherein said couper is benzoylaceto-Z-methoxy-S-hexadecyloxycarbonyl anilide.

. 5. The color photographic material as claimed in claim 1 wherein said coupler is benzoylaceto-Z-chloro-5-dodecyloxycarbonyl anilide.

6. The color photographic material as claimed ,in claim 1 wherein said coupler is benzoylaceto-2-chloro-5-(2- ethylhexyloxy carbonyl) anilide.

7. The color photographic material as claimed is claim 1 wherein said coupler is benzoylaceto-Z-chloro-S-(8,8-dimethyloctyloxy carbonyl) anilide.

8. The color photographic material as claimed in claim References Cited 1 wherein said coupler is benzoylaceto-Z-chloro-S (2,2-di- UNITED STATES PATENTS methyldecyloxy carbonyl) anilide.

9. The color photographic material as claimed in claim 2,418,747 4/1947 Bavley 96-400 1 wherein said coupler is benzoylchloroaceto-2-methoxy- 5 2,908,573 10/1959 Bush et 96-400 S-dodecycloxycarbonyl anilide.

10. The color photographic material as claimed in NORMAN TORCHIN' Examme" claim 1 wherein said alkyl group having at least eight I. T. BROWN, Examiner. carbon atoms has at least one side chain. s PICO Assistant Examiner. 

